Washable color changing compositions

ABSTRACT

A washable multiple coloring composition system is disclosed whose coloring effect is changed upon treatment with a second coloring composition, once the second coloring composition has been deposited over the undercolor coloring composition. The washable multiple ink system comprises: 
     (a) an undercolor aqueous coloring composition comprising a compatable surfactant in an amount sufficient to provide washability and an undercolor dye whose coloring ability is destroyed in the presence of a pH of about 10 or greater and/or by a reducing agent; and 
     (b) an overcolor aqueous coloring composition comprising a compatable surfactant in an amount sufficient to provide washability, a colorant capable of maintaining its characteristic color in the presence of a pH of about 10 or greater and/or a reducing agent, a base in an amount sufficient to yield a pH of the overcolor composition of about 10 or greater, and/or a reducing agent.

RELATED APPLICATIONS

This application is a continuation-in-part of previous U.S. patentapplication Ser. No. 08/089,503, now U.S. Pat. No. 5,326,388 which was acontinuation-in-part of previous U.S. patent application Ser. No.07/923,308 which issued as U.S. Pat. No. 5,232,494 on Aug. 3, 1993. Thisapplication is also a continuation-in-part of U.S. patent applicationSer. No. 08/078,722, now U.S. Pat. No. 5,352,282 which was acontinuation of previous U.S. patent application Ser. No. 07/923,308which issued as U.S. Pat. No. 5,232,494 on Aug. 3, 1993.

FIELD OF THE INVENTION

This invention relates generally to the field of coloring compositionsand more particularly to a pair of washable coloring compositions whichmay be used in conjunction with each other to enable laying down aninitial mark using a first undercolor coloring composition yielding afirst color and then using an overcolor coloring composition to enable achange of color of a portion or the entirety of the initial mark, bothof which marks may be easily washed away from skin and fabric.

BACKGROUND OF THE INVENTION

Children enjoy various drawing and coloring activities using a varietyof mediums. Useful in such activities are markers containing inks,crayons, pencils of various colors, and various paints including watercolors, oil paints and acrylic paints. However, children would oftenlike to change the color of a mark after they have made the mark. Oneinstance would be the desire to add a yellow sun over a previouslycolored blue sky.

Changing the color of a mark is not readily done with the typicalchildren'scoloring instruments such as those described. In the past,children changed the marks by placing the mark of one color over themark of another color. When performing this using traditional markingpens, the marks produced are often not the desired colors and the tipsof the markers get soiled with the other inks, rendering the markeruseless, If attempted with traditional children's paints, the colorstend to bleed together resulting in undesirable color smears. Therefore,there has been a long felt need for coloring compositions, includingpaints, inks, and markers containing such compositions, which producemarks of a first color that can be readily changed into a wide varietyof second colors. Especially needed is such a group of compositionswhich may be used in markers without soiling the nib of the second usedmarking instrument.

Coloring compositions generally are mixtures of a coloring matterdispersed or dissolved in a carrier fluid. The colorant, if readilydissolving in the carrier fluid, is termed a dye. An insoluble coloringmaterial is termed a pigment. Pigments are finely ground solid materialsand the nature and amount of pigment contained in an ink determines itscolor.

In one available marker application, a child is able to change aspecific initial mark laid down to a second specific color by applying areducing agent to the first mark yielding a change in color. The markerinks used in these markers are typically prepared by blending a reducingagent (sometimes termed a bleaching agent) or pH sensitive dye with adye that is stable in the presence of a reducing agent or high pH. Forexample, German Patent Specification No. 2724820, (hereinafter "theGerman Patent"), concerns the combining of a chemically stable dye and achemically unstable dye in an ink formulation. Once a mark using thiscombination of stable and unstable dyes is laid down, the mark may beoverwritten with a clear reducing agent solution, eliminating the colorcontribution of the unstable dye. The resulting mark of the stable dye,with its characteristic color, remains.

There are several drawbacks to such a marking system. First, there arestrict limitations on the number of color changes which may be produced.Specifically, in formulations made according to the German Patent, theparticular ink composition may only be changed from a first color to afixed second color. For example, a green mark may only be changed to aviolet color as the inks are described in the practice of the GermanPatent. In addition, since one of the required pair of markers containsonly the reducing agent, that reducing agent marker cannot render avisible mark and may only be used in combination with the base colormarker. Once the base color marker is used up, the reducing agent markeris of no use. Or, once the reducing agent marker is used up, the basecolor marker may only be used for the color which it initially markswith. A further disadvantage of the marking process of the German Patentis that the nib of the reducing agent marker tends to get soiled bypicking up the colors of the base coloring composition, thus taintingthe color of subsequent marks.

A further disadvantage to such previous marking systems is that they arenot washable and thus not easily removed from skin, fabric or othersurfaces. It is well known that a major deficiency of children'scoloring markers is their propensity to leave enduring stains on bothskin and clothing. While permanence is a desirable characteristic of theso-called "permanent" markers, it is one of the most objectionable ofproperties for coloring instruments used by young children. Accordingly,much effort has been expended over many years by producers of theseinstruments to reduce or eliminate staining. This is attested to by therather numerous offerings of so-called "washable" markers, which onclose examination, are found to remove very poorly from fabrics that aretypically used in children's clothing. Most such markers achieve theirlimited washability by utilizing dyes which have good fugitivity fromfabrics and by utilizing lowered dye concentrations in an effort tominimize skin staining. In all cases, however, these "washable" productsleave objectionable stains on the skin. The inks used in such markerstherefore lack fugitivity from skin.

Coloring compositions may optionally include such ingredients ashumectants, preservatives, and drying agents. Humectants function toimprove freeze/thaw stability and to control drying out of the tip whenthe coloring composition is used as a marker ink. Preservatives servethe obvious function of preventing spoilage of the ink during theexpected shelf life of the marker product. Drying agents speed drying ofa mark laid down by a marker.

Therefore, an object of the present invention is to provide a washablecoloring composition system which is capable of enhanced multiple colorchanging abilities.

An additional object of the present invention is to produce a washablecoloring composition system which includes at least two differentcoloring compositions each of which may be used independently or whichmay be used in combination to provide color changing ability.

A further object of the present invention is to provide a washablecoloring composition system in the form of inks which prevents a nib ofa color changing marker from becoming visibly soiled from contacting abase color composition.

A still further object is to provide a coloring composition which, inaddition to being washable from the skin, is more easily washable fromfabrics.

These and other objects will become apparent to those skilled in the artto which the invention pertains.

SUMMARY OF THE INVENTION

The present invention overcomes the drawbacks associated with prioroverwriting ink compositions in that the particular undercolor coloringcomposition made according to the invention may be changed to multiplesecond colors, depending upon the dye present in the overcolorcomposition.

Advantageously, an overcolor coloring composition of the presentinvention makes a visible mark, thus it may be used alone or incombination with an undercolor coloring composition.

An additional advantage of the overcolor coloring composition of thepresent invention when used as an ink is that, unlike prior used colorchange markers, the nib of the marker containing the overcolor coloringcomposition does not become visibly soiled with the undercolor coloringcomposition color because the undercolor is immediately destroyed uponcontact with the overcolor composition.

A further advantage of the overcolor and undercolor compositions of thepresent invention is that these compositions are washable from the skin,fabric and other surfaces.

In general, the present invention is a washable multiple coloringcomposition system wherein an undercolor coloring effect may be changedupon treatment with an overcolor second coloring composition. In oneembodiment, the washable multiple coloring composition system comprises:

(a) an undercolor aqueous coloring composition comprising a surfactantin an amount sufficient to provide washability and an undercolor dyewhose coloring ability is destroyed in the presence of a pH of about 10or greater and/or in the presence of a reducing agent; and

(b) an overcolor aqueous coloring composition comprising a surfactant inan amount sufficient to provide washability, a colorant capable ofmaintaining its characteristic color in the presence of a pH of about 10or greater and/or in the presence of a reducing agent, and a base suchthat the pH of the overcolor composition is about 10 or greater and/or areducing agent.

Suitable surfactants which provide washability to the compositions ofthe present invention include Dowfax 3B2, Tamol SN and Polytergent BN.

Also disclosed is a washable ink composition system comprising:

(a) an undercolor aqueous ink comprising a surfactant in an amountsufficient to provide washability and an undercolor dye whose coloringability is destroyed in the presence of a reducing agent and/or a pH ofabout 10 or greater in an amount of from about 0.1 to about 15% byweight of the undercolor ink; and

(b) an overcolor aqueous ink comprising from about 20% to about 55% of asurfactant which provides washability; from about 1% to about 20% byweight of said overcolor ink of a reducing agent; from about 0.1% toabout 10% by weight of said overcolor ink of a base; and from about 0.1%to about 15% by weight of said overcolor ink of a colorant whichmaintains its characteristic color in the presence of a reducing agentand/or a pH of about 10 or greater.

A washable color changing marking system is also disclosed whichcomprises at least two marking instruments. The washable undercolormarking instrument contains an undercolor ink composition comprising asurfactant which provides washability to the composition and a dye whosecoloring ability is destroyed in the presence of a reducing agent and/ora pH of about 10 or greater. The washable overcolor writing instrumentcontains an overcolor ink. The overcolor ink comprises (1) from about20% to about 55% of a surfactant which provides washability; (2) fromabout 1% to about 20% by weight of reducing agent; (3) from about 0.1%to about 10% by weight of a base; and (4) from about 0.1% to about 15%by weight of a colorant which maintains its characteristic color in thepresence of a reducing agent and/or a pH of about 10 or greater.

The coloring compositions of the invention may also optionally comprisea humectant, a drying agent, and a preservative.

DETAILED DESCRIPTION OF THE INVENTION

The present invention imparts the desirable ease of application andconvenience of use of traditional color changer systems while avoidingthe strict limitations of current color change markers. The compositionof the present invention therefore imparts improved and convenientcoloring properties as well as washability.

In general, the present invention is a washable multiple coloringcomposition system wherein the color of a mark laid down by anundercolor coloring composition, for example using a marker to dispensethe composition, may be overwritten by a variety of second colors usingan overcolor coloring composition over the undercolor coloringcomposition. An embodiment of this washable marking system comprises:

(a) an undercolor aqueous coloring composition comprising a surfactantin an amount sufficient to provide washability to said undercoloraqueous coloring composition and an undercolor dye whose coloringability is destroyed in the presence of a reducing agent and/or a pH ofabout 10 or greater; and

(b) an overcolor aqueous coloring composition comprising a surfactant inan amount sufficient to provide washability to said overcolor aqueouscoloring composition, a colorant capable of maintaining itscharacteristic color in the presence of a reducing agent and/or a pH ofabout 10 or greater, and a reducing agent and/or a base in an amountsufficient to yield a pH of about 10 or greater.

To increase the pH of the overcolor aqueous coloring composition, a basein an amount sufficient to elevate the pH of the overcolor aqueouscoloring composition to a level of about 10 or greater, and preferablyfrom about 10 to about 12, is preferably used.

In a preferred embodiment, the overcolor aqueous coloring compositioncomprises both a reducing agent and a base in an amount sufficient toelevate the pH of the overcolor aqueous coloring composition to about 10or greater and preferably from about 10 to about 12. Preferably, theovercolor composition has a high pH and a reducing agent so that thetype of undercolor is unimportant. In this preferred embodiment, thewashable marking system comprises:

(a) an undercolor aqueous coloring composition comprising a surfactantin an amount sufficient to provide washability and an undercolor dyewhose coloring ability is destroyed in the presence of a reducing agentand/or in the presence of a pH of about 10 or greater; and

(b) an overcolor aqueous coloring composition comprising from about 20%to about 55% of a surfactant; from about 1% to about 20% by weight of areducing agent, a base in an amount sufficient to produce a pH of about10 or greater, and from about 0.1% to about 15% by weight of a colorantcapable of maintaining its characteristic color in the presence of areducing agent and a pH of about 10 or greater.

Finally, a collection of washable multiple undercolor coloringcompositions may be assembled, some of which contain a dye incapable ofmaintaining its characteristic color in the presence of a pH of about 10or greater and some of which contain a dye incapable of maintaining itscharacteristic color in the presence of a reducing agent. For economicefficiency, in formulating overcolors for use with such a collection ofundercolors, it is preferable to use an overcolor coloring compositionwhich comprises (1) a surfactant which confers washability; (2) acolorant capable of maintaining its characteristic color in the presenceof both a pH of about 10 or greater and a reducing agent, (3) a base,and (4) a reducing agent. In such a case, the overcolor coloringcomposition may be used to overwrite a mark made by any of thecollection of undercolor coloring compositions without regard to whetherthe undercolor composition contains a dye which is incapable ofmaintaining its characteristic color in either the presence of anelevated pH or in the presence of a reducing agent.

A surfactant is present in the undercolor coloring compositions of thepresent invention to impart washability to the compositions. Anycompatible surfactant which confers such washability is suitableprovided excessive strike through does not result. Examples of suitablesurfactants include anionic surfactants such as disulfonated productsmanufactured by The Dow Chemical Company and sold under the trademarkDowfax, specifically Dowfax 3B2 and Dowfax 8390, sodium naphthalenesulfonate which is manufactured by Rohm & Haas and sold under thetrademark Tamol SN, and a proprietary product which is manufactured byOlin Chem and sold under the trademark Polytergent BN (U.S. Pat. No.5,262,535), and the surfactant disclosed and claimed in U.S. Pat. No.5,262,535 which is incorporated herein by reference. Other surfactantswhich contribute to washability of the undercolor coloring compositionsare identified in Table I as disclosed in U.S. Pat. No. 5,116,410, whichis incorporated herein by reference.

                  TABLE I                                                         ______________________________________                                        Surfactant (Source)                                                                            Chemical Description                                         ______________________________________                                        Aristonate 430   sodium alkyl benzene                                         (Pilot Chemical Co.)                                                                           sulfonate                                                    Aristonate 460   sodium alkyl benzene                                         (Pilot Chemical Co.)                                                                           sulfonate                                                    Aristonate 500   sodium alkyl benzene                                         (Pilot Chemical Co.)                                                                           sulfonate                                                    Blancol N        sodium salt of sulfonated                                    (GAF Corp.)      naphthalene - formaldehyde                                                    condensate                                                   Conco Sulfate 2A1                                                                              sodium alkyl dipenyl oxide                                   (Continental Chemical Co.)                                                                     sulfonate                                                    Darvan #2        sodium salts of polymerized                                  (R. T. Vanderbilt Co.)                                                                         substituted benzoid alkyl                                                     sulfonic acids                                               Darvan 404       calcium salts of                                             (R. T. Vanderbilt Co.)                                                                         polymerized substituted                                                       benzoid alkyl sulfonic                                                        acids                                                        Daxad 11         sodium salts of polymerized                                  (W. R. Grace Co.)                                                                              alkyl naphtalenic sulfonic                                                    acids                                                        Daxad 17         sodium salts of polymerized                                  (W. R. Grace Co.)                                                                              alkyl naphthalenic sulfonic                                                   acids                                                        Daxad 19         sodium salts of polymerized                                  (W. R. Grace Co.)                                                                              alkyl naphthalenic sulfonic                                                   acids                                                        Daxad 23         sodium salts of polymerized                                  (W. R. Grace Co.)                                                                              alkyl naphthalenic sulfonic                                                   acids                                                        Kara Sperse DDL  sodium organic sulfonate                                     (Lyndal Chemical Co.)                                                         Kara Sperse DDL-12                                                                             modified sulfonate                                           (Lyndal Chemical Co.)                                                         Lomar D          sodium salt of condensed                                     (Diamond Shamrock Co.)                                                                         mononaphthalenic sulfonic                                                     acids                                                        Lomar LS         sodium salt of condensed                                     (Diamond Shamrock Co.)                                                                         mono naphthalenic sulfonic                                                    acids                                                        Petro-D-425      sodium salt of sulfonated                                    (DeSoto Inc.)    naphthalene formaldehyde                                                      condensate                                                   Stepantan A      condensed naphthalene                                        (Stepan Co.)     sulfonate                                                    Turkey red oil   sulfated castor oil                                          ______________________________________                                    

The most preferable surfactant for use in the washable compositions ofthe present invention is Dowfax 3B2. Dowfax 3B2 is a diphenyl oxidedisulfonate having tough cleaning product applications, particularly onsynthetic fabrics as well as cotton and synthetic blends.

Not all surfactants confer washability on the undercolor coloringcompositions of the present invention. For example, non-ionicsurfactants and aliphatic sulfonates have not been found to be effectivesurfactants for the coloring compositions of the present invention.

The surfactant should be present in an amount which is sufficient toimpart washability to the coloring compositions. Generally, 20% byweight may be sufficient, but as much as 55% may be desirable.Preferably, a surfactant content of about 25% to about 35% by weight ispresent, and most preferably about 28% to about 32% by weight.

Use of citric acid or other antioxidants may be desirable for theseundercolor formulations because it helps dye stability. It may alsoassist washability of the coloring compositions from fabric and is thus,preferably present in undercolor compositions.

Most suitable for use as dyes in the undercolor coloring compositionsare dyes whose coloring capabilities are easily destroyed by a reducingagent. Such coloring compositions are commonly known in the field andare occasionally used as chemically "erasable" inks. Also suitable foruse as dyes in the undercolor coloring compositions are dyes whosecoloring capabilities are easily destroyed in the presence of a pH ofabout 10 or greater. Dyes must also be compatible with the surfactant.Especially suitable for use as dyes in the undercolor coloringcomposition are polymethine dyes, triphenylmethane dyes, cyanine dyes,methine dyes, and azo dyes which are unstable in the presence of a pH ofabout 10 or greater and/or are unstable in the presence of a reducingagent. Such dyes include the dyes marketed under the tradenames BASACRYLX-RL YELLOW™ (Basic Yellow 49), marketed by the BASF Corporation,ASTRAZON BLUE FRR™ (Basic Blue 69), ASTRAZON BRILLIANT RED 4G™ (BasicRed 14), and ASTRAZON PINK FBB™ (Basic Red 49) by Miles(Mobay); and thedyes marketed under the tradenames Acid Green 3 by InternationalDyestuffs Corporation, Acid Blue 93 and Acid Violet 19 marketed bySpectra Color Corporation as well as mixtures thereof.

The listed ASTRAZON dyes are classified as polymethine dyes. Polymethinedyes are colored substances in which a series of --CH═ (methine) groupsconnect to terminal groups of a chromophore. Polymethine and cyanine areoften used interchangeably as generic terms for all polymethine dyes.The previous primary usage for polymethine dyes are dying acetate rayonas well as polyacrylnitrile and polyacrylamide. Acid Green 3, Acid Blue93 and Acid Violet 19 are triphenylmethane dyes. Acid Green 3 iscommonly used in making pulp colors or lakes. Acid Violet dyes areprimarily fashion colors.

To achieve good coloring of the undercolor coloring composition, theminimum concentration of dye which will produce a workable ink isgoverned by the color intensity desired, though as little as 0.1% dyemay be sufficient for certain applications. The maximum workableconcentration of dye is determined largely by the ability to maintain astable composition and the depth of color desired and can vary widelydepending upon the concentration of other components. It is also afunction of the characteristics of the desired end product, though apractical upper limit in the formulation of, for example, a marker ink,is about 15% by weight. The preferred concentration range for mostapplications is from about 1% to about 6% dye by weight of thecomposition. A concentration of about 1.5% to about 4% is even morepreferred when the undercolor coloring composition is to be used as anink for a typical marker to ensure good coloration.

The overcolor coloring composition of the present invention ispreferably formulated by combining a surfactant, a reducing agent and abase with a colorant which maintains its characteristic color in thepresence of reducing agent and in high pH conditions. Of course, wherecolorants used in the undercolor composition are only affected by areducing agent, the base may be deleted. Also, where dyes used in theundercolor composition are only affected by an elevated pH, the reducingagent may be eliminated. However, for maximum commercial application andfor maximum effect upon a wider variety of undercolor compositions, theovercolor composition is preferably formulated with a reducing agent andbase in combination.

A limited number of dye colorants meet this criteria. Dyes to be used inthe overcolor coloring composition must be highly resistant to chemicalattack such as from a reducing agent or high pH conditions. Dyes meetingthis criteria include xanthene dyes, pthalocyanine dyes, and azo dyeswhich are stable in the presence of a pH of about 10 or greater and/orare stable in the presence of a reducing agent. Dyes which have beenfound to meet these criteria include PYRANINE 120™ (which is commonlyknown as Solvent Green 7) marketed by Miles(Mobay), Acid Red 52 marketedby Carolina Color, Food Red 14 marketed by Hilton-Davis, BASANTOL GREEN910™ (which is commonly known as Acid Green 26) marketed by BASF, AcidRed 87 marketed by Hilton-Davis, Acid Red 92 marketed by InternationalDyestuffs Corporation, Acid Red 388 and Direct Blue 199 marketed byCrompton & Knowles, and mixtures thereof.

Acid Red dyes, classified as xanthene dyes, are generally used ascolorants for foods, drugs and cosmetics. Specifically, Acid Red 87, isthe disodium salt of 2,4,5,7 -tetrabromo-9-o-carboxyphenyl-6-hydroxy-3-isoxanthone. Acid Red 87 is also called D & C Red No. 22 by the Foodand Drug Administration ("FDA"), and sold under the tradenames Eosine YSand Eosine G. In addition, Acid Red 92, the disodium salt of2,4,5,7-tetrabromo-9-3,4,5,6tetrachloro-o-carboxylphenyl)-6-hydroxy-3-isoxanthone, is called D & CRed No. 28 by the FDA, and sold under the tradename Phloxine B. Acid Red52 is a colorant for plastics. Further, Food Red 14 or FD&C Red No. 3,commercially available under the tradenames Erythrosine and ErythrosineBluish, is the disodium salt of9(o-carboxyphenyl)-6-hydroxy-2,4,5,7-tetraiodo-3H-xanthen-3-one, whichcontains smaller amounts of lower iodinated fluoresceins.

To achieve good coloring of the overcolor coloring composition, theminimum concentration of dye which will produce a workable ink isgoverned by the color intensity desired, though as little as 0.1% dyemay be sufficient for certain applications. The maximum workableconcentration of dye is determined largely by the ability to maintain astable composition and the depth of color desired and can vary widelydepending upon the concentration of other components. It is also afunction of the characteristics of the desired end product, though apractical upper limit in the formulation of, for example, a marker ink,is about 15% by weight. The preferred concentration range for mostapplications is from about 1% to about 6% dye by weight of thecomposition. A concentration of about 1.5% to about 4% is even morepreferred when the overcolor coloring composition is to be used as anink for a typical marker to ensure good coloration.

A surfactant is present in the overcolor coloring compositions of thepresent invention to impart washability to the compositions. Anycompatible surfactant which confers such washability is suitableprovided excessive strike through does not result. Examples of suitablesurfactants include anionic surfactants such as disulfonated productsmanufactured by The Dow Chemical Company and sold under the trademarkDowfax, specifically Dowfax 3B2 and Dowfax 8390, sodium naphthalenesulfonate which is manufactured by Rohm & Haas and sold under thetrademark Tamol SN, and a proprietary product which is manufactured byOlin Chem and sold under the trademark Polytergent BN. Other surfactantswhich contribute to washability of the undercolor coloring compositionsare identified in Table I. The most preferable surfactant for use in thewashable compositions of the present invention is Dowfax 3B2. Dowfax 3B2is a diphenyl oxide disulfonate having tough cleaning productapplications, particularly on synthetic fabrics as well as cotton andsynthetic blends.

Not all surfactants confer washability on the undercolor coloringcompositions of the present invention. For example, non-ionicsurfactants and aliphatic sulphonates are not effective surfactants forthe coloring compositions of the present invention.

The surfactant should be present in an amount which is sufficient toimpart washability to the coloring compositions. Generally, 20% byweight may be sufficient, but as much as 55% may be desirable.Preferably, a surfactant content of about 25% to about 35% by weight ispresent, and most preferably about 28% to about 32% by weight.

Typical reducing agents for use in the overcolor coloring composition ofthe invention include hydrogen sulfide, sodium sulfite, sodiumbisulfite, and stannous chloride. Certain limited bleaches which act asweak oxidizing agents such as sodium hypochloride and hydrogen peroxidemay also operate to effect a color change. Hydrogen peroxide is alsoknown to sometimes operate as a weak reducing agent. The preferredreducing agent for use in the coloring composition of the invention isNa₂ SO₃ (sodium sulfite). Reducing agent is generally present in theovercolor coloring composition of the invention in an amount from about1% to about 20% with a minimal amount required to allow for theelimination of the undercolor coloring composition of the invention andthe maximum amount determined by the stability of the composition andthe safety of the composition for use by children. Preferably, thereducing agent is contained in the overcolor coloring composition in anamount of from about 5% to about 15%, and most preferably in an amountof from about 8% to about 12% by weight of the overcolor coloringcomposition.

Overcolor coloring compositions of the invention may be formulated usingonly a reducing agent. However, the reducing agents used in overcolorcoloring compositions of the invention perform most effectively in thepresence of an elevated pH. To elevate the pH of the overcolor coloringcomposition, a base is added. Bases which may be used in the overcolorcoloring composition of the invention are typically strong bases,usually having a pH of from about 10 to about 12. Typical bases whichmay be employed in the overcolor coloring composition of the inventioninclude ammonium hydroxide, sodium hydroxide, and sodium carbonate. Thepreferred base is sodium hydroxide.

The base is generally present in the overcolor coloring composition ofthe invention in an amount from about 0.1% to about 20% by weight.Preferably, the base is added in an amount sufficient to raise the pH ofthe composition to a pH of from about 10 to about 12. Preferably, thebase is contained in the overcolor coloring composition in an amount offrom about 5% to about 15%, and most preferably from about 10% to about12% by weight of the overcolor coloring composition.

The water used in the undercolor coloring composition and the overcolorcoloring composition of the invention present invention is preferablydeionized water. The amount of water present in undercolor coloringcompositions is typically from about 10% to about 90% and this amount isin large part determined by the desired end use of the undercolorcoloring composition, for instance, as an ink or a paint, and the amountof other components included in the undercolor color composition. Toachieve a desirable viscosity when the undercolor coloring compositionis used in the form of, for example, an ink, water is preferably presentin an amount of from about 20% to about 80%, and most preferably fromabout 45% to about 60% by weight of the composition.

The amount of water present in the overcolor coloring composition of theinvention is also governed in large part by the desired end use of thecomposition, for instance, as an ink or a paint, and the amount of othercomponents included in the undercolor coloring composition. The amountof water present in overcolor coloring compositions is typically fromabout 10% to about 90%. To achieve a desirable viscosity when theovercolor coloring composition is used in the form of, for example, anink, water is preferably present in an amount of from about 20% to about80%, and most preferably from about 45% to about 60% by weight of thecomposition.

Optionally, both the undercolor coloring composition and the overcolorcoloring composition may further comprise such additives as humectants,drying agents and preservatives such as biocides and fungicides.

Addition of a humectant ensures that coloring compositions of theinvention, when in the form of an ink, do not prematurely dry in acapillary marking system, such as a bonded fiber marking nib. Typicalhumectants which may be employed in the coloring compositions of thepresent invention include polyhydric alcohols such as ethylene glycol,propylene glycol, hexylene glycol and poly(ethylene glycol), andhydroxylated starches. The humectant is preferably glycerin.

The humectant is generally used in an amount of from about 0% to about30% by weight of the composition, though this range is by no meanscritical. The amount of humectant to be added is determined by the typeof nib used in the writing or marking instrument to be employed and theprotection time period desired. In one preferred composition, thehumectant, glycerin, is added in an amount of from about 3% to about 15%by weight of the coloring composition.

To achieve a more rapid drying rate and to improve markingcharacteristics upon nonporous materials, a drying agent may be added toincrease the overall volatility and therefore the evaporation rate ofthe water and the pH regulant. Any compatible material which performsthis function may be used.

The drying agent preferably should be a volatile polar material so as toensure compatibility with the primary components of the marker ink.Straight chain C2-C4 alcohols are good, highly volatile drying agents,and of these, ethanol is preferred because of its relatively low costand because it does not contribute any unpleasant odor to thecomposition. Alcohols can also provide added benefits, such as reducingsurface tension, increasing adherence of the ink to porous surfaces, andproviding bactericidal activity when added to the ink composition.

To discourage improper usage of the marker ink, such as ingesting theink, the alcohol may contain a bittering agent or a conventionaldenaturant. An alcohol utilizing a bittering agent will discourage suchimproper usage of the ink by simply imparting a disagreeable taste,while not requiring the use of toxic denaturants as methanol or benzene,and is therefore preferred. A conventional denatured alcohol may, ofcourse, also be utilized. The most preferred drying agent is an ethylalcohol which contains a bittering agent and which is sold under thetrade name SDA 40B, manufactured by Aaper Alcohol.

When utilized, the drying agent preferably is added from about 5% up toabout 30% by weight, with the most preferred concentration being about8-10% by weight, though these amounts are not critical to the practiceof the invention. About 8% per weight of drying agent is ordinarilyrequired to ensure rapid drying of the ink on a nonporous surface, whileamounts in excess of about 30% by weight may adversely affect stabilityof the ink and may cause flocculation of the pigment unless otherstabilizing additives are employed.

To maintain the shelf life of the composition, a preservative may beadded. The preservative preferably serves as both a bactericide and afungicide, and is added in any effective amount, though a typicalconcentration range is from about 0.1% up to about 5.0% by weight. Theuse of preservatives in levels greater than about 5% by weight may causethe ink to become toxic or unstable and may, in any event, beunnecessary. Should alcohol be added to the composition as a dryingagent, that alcohol will function as a preservative to some extent also.

Any conventional preservative may be utilized in the invention as longas there is compatibility with the remaining ink components. Forexample, preservatives manufactured by Dow Chemical Co. and sold underthe trademarks Dowicil 75(1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride) and Dowicil200 (3-chlorovinyl-hexamethylene tetrammonium chloride) or apreservative manufactured by Rohm and Haas and sold under the trademarkKathon PFM (isothiazolinones), or a preservative manufactured by SuttonLabs and sold under the trademark Germall II (imazolidinyl urea), or apreservative manufactured by Merck and sold under the trademark Tektamer38 (1,2 dibromo-2,4-dicyanobutane), will work in the composition of theinvention.

Other acceptable preservatives include TROYSAN POLYPHASE P100™, a3-Iodo-2-Propynyl Butyl Carbamate sold by Troy Chemical commonlycombined in solution with PVP K-30™, a 2-Pyrrolidinone, 1-Ethenyl-,Homopolymer solubilizer ((C₆ MgNO)_(x) sold by ISP Technologies Inc.,and M-PYROL™, a 1-Methyl-Pyrrolidinone solubilizer sold by GAF ChemicalsCorporation. Addition of preservatives to the undercolor and overcolorcoloring compositions inhibits the growth of bacteria and fungi inwater-based products.

Typically, a child may make marks or color a picture using one or moremarkers containing various undercolor coloring compositions on asuitable substrate, such as paper. The child may then select one or moremarkers containing various overcolor coloring compositions of theinvention. The child may then overwrite a portion or all of thepreviously made markings eliminating the color of the undercolorcoloring composition as applied and leaving only the color of theovercolor coloring composition used to overwrite the undercolor colorcomposition. Because of the surprisingly strong and immediate impact ofthe overcolor coloring composition used to overwrite the undercolorcoloring composition, the overcolor marker appears to paint a color overthe undercolor on the portions of the substrate on which it is applied.

A child may also apply the overcolor coloring composition directly tothe substrate. If an undercolor coloring composition is then used tooverwrite the mark laid down by the overcolor coloring composition, theovercolor coloring composition will eliminate the color contributed bythe undercolor coloring composition leaving only the color of theovercolor coloring composition where that mark was previously made. Theundercolor color will be seen on other locations on the substrate. Thischange has been observed to occur more slowly than when the overcolorcoloring composition is applied over the undercolor coloringcomposition. This slowed reaction is presumably caused by thepenetration of the overcolor coloring composition into the papersubstrate. The child gains great play benefit by viewing this slowlydisappearing color.

Preferably, when the coloring compositions of the invention are used inthe form of inks, the inks are placed in conventional markers using suchnibs as bonded fiber or sintered plastic. Various undercolor coloringcompositions are placed in an undercolor set of markers, each containingan appropriate different color dye. Various overcolor coloringcompositions of the invention are placed in a second group of markers,each of these compositions containing an appropriate different colorcolorant, either a dye or pigment.

Preferably, when the coloring compositions of the invention are used inthe form of inks, the inks are placed in conventional markers. Thesemarkers utilize reservoirs for storing the ink and nibs to dispense theink. Typically, an ink reservoir contains a sponge like reservoir whichhold the thee ink. The preferred reservoirs for undercolor coloringcompositions of the invention are made of acetate, polyester orpolypropylene. The preferred reservoirs for overcolor coloringcompositions of the invention are made of polypropylene which moresuitably resists attack by any reducing agent contained in the overcolorcoloring composition.

In general, any suitable nib may be used in conjunction with theundercolor coloring compositions of the invention. However, where nylonor polyamide fibers are used, they should be checked for preferentialdye absorption. Also, any compatible nib may be used in conjunction withthe overcolor coloring compositions of the invention. Sinteredpolyethylene nibs are preferred and nylon and polyamide nibs should bechecked for preferential dye absorption. In general, bonded polyesterfiber nibs are not suitable for use with the overcolor coloringcompositions of the invention. Various undercolor coloring compositionsare placed in an undercolor set of markers, each containing anappropriate different color dye. Various overcolor coloring compositionsof the invention are placed in a second group of markers, each of thesecompositions containing an appropriate different color colorant, eithera dye or pigment. A marking kit or system is thus formed which comprisesboth overcolor coloring compositions and undercolor coloringcompositions.

The washable coloring compositions of the present invention may becontained in a marker having a reservoir and a nib wherein the reservoircontains an undercolor aqueous coloring composition comprising acompatable surfactant in an amount sufficient to confer washability andan undercolor dye whose coloring ability is destroyed in the presence ofa ph of about 10 or greater, or an overcolor aqueous compositioncomprising a compatable surfactant in an amount sufficient to conferwashability, a colorant capable of maintaining its characteristic colorin the presence of a pH of about 10 or greater and an effective amountof a reducing agent and/or base sufficient to yield a pH of about 10 orgreater.

EXAMPLES Test Procedures

A. The fugitivity from skin of the compositions of the invention wasmeasured by the following test:

1. Wash hands with soap and warm water. The pre-stain cleansing removesexcess oil and dirt from the skin and provides a more consistent skinsurface for testing. Allow the skin to dry for 30 seconds.

2. In the case of a marker, draw a stripe on the palm of the hand withthe flat side of the nib. In the usual case, a 1/4 inch wide by 1 inchlong stripe works well. Apply enough pressure and/or multiple passes todevelop a stripe with good color intensity. If it is desired to make acomparison among two or more compositions, more than one stripe may bedrawn. Let stripes dry for one minute.

3. Place hand under tap and briefly rinse off excess ink with warmwater.

4. Wash hands with soap in the following manner: lather using a minimumamount of soap; replace soap in soap dish; rub hands together brisklywith modest pressure for 30 seconds; rinse away soap.

5. Wipe hands dry with paper towels, and complete the drying with arelatively dry towel. A dry towel will help to rub off residual tracesof ink.

6. Evaluate removability from skin by assigning a score of between 1 and5, with a score of 1 indicating essentially complete removability and ascore of 5 indicating essentially no removability.

7. If removal of the marks is incomplete, repeat steps 4 through 6.

B. The fugitivity from fabric of the compositions of the invention wasmeasured by the following test.

1. Cut test swatches of a standard white 50% cotton, 50% polyesterfabric to 6"×7" (15.2 cm×17.8 cm) to identify fabric direction.

2. Pre-washed swatches with bleach, non-staining water softener andordinary household phosphate detergent powder using 120˜F hot water asdirected in ASTM D4265-83.

3. Pull test swatches taut in a 12.5 cm diameter embroidery hoop.

4. Deposit marker inks dropwise onto the fabric onto a circular areaabout 8 cm in diameter. If the ink chromotographs to give a stronglycolored ring at the circumference of the stained circle, pre-wet thefabric adjacent to the hoop with water so that inward wicking of thewater counteracts the outward wicking of the ink. Permit the stainedarea to expand to its equilibrium diameter prior to drying.

5. Remove the stained sample from the hoop and allow to "age" for apredetermined time (usually 24 hours).

6. Staple a group of stained swatches with heavy duty staples to theedges of a bath towel. Rinse in cold water to remove excess dye.

7. Add a dummy load of unstained fabrics to provide a four pound washload. Wash the load for 12 minutes with a hot (120˜F)/cold cycle.

8. Dry the load in a dryer.

9. Detach the test swatches from the carrier towel, iron, and measuretheir color on the colorimeter.

Evaluation of Test Data

Skin fugitivity data are based on a visual rating system as follows:

5=severe

4=moderate

3=slightly more visible

2=slightly visible

1=barely visible

0=no stain

For each additive screened, skin fugitivity was improved over thecontrol, which was rated at 2.

Fabric fugitivity data, stated in terms of E values, correspond tovisual observations as follows:

    ______________________________________                                        E = up to 2.2       no visible stain                                          E = 2.20-2.90       trace                                                     E = 2.90-4.90       slight                                                    E = 4.90-6.40       moderate                                                  E = over 6.40       heavy                                                     ______________________________________                                    

For most additives screened, at least a modest increase in fabricfugitivity was observed.

Coloring Compositions

Examples of marking systems of the present invention when formulated asan ink are as follows. Quantities are in percent by weight of the totalcomposition.

    ______________________________________                                        Undercolor Color Ink Examples                                                 ______________________________________                                                        Example 1 Example 2                                                           Red Ink   Green Ink                                           Component       %         %                                                   ______________________________________                                        Deionized Water 53.7      53.7                                                Dowfax 3B2      30.0      30.0                                                Glycerin        10.0      10.0                                                Preservative                                                                  Premix                                                                        M-Pyrol         2.4       2.4                                                 PVP 30          0.05      0.05                                                Troysan                                                                       Polyphase P-100 0.05      0.05                                                Nuosept         0.5       0.5                                                 Citric Acid     0.3       0.3                                                 Dye                                                                           Basic Red 14    3.0       --                                                  Acid Green 3    --        2.0                                                 ______________________________________                                                        Example 3 Example 4                                                           Blue Ink  Black Ink                                           Component       %         %                                                   ______________________________________                                        Deionized Water 53.7      53.7                                                Polytergent BN  30.0      30.0                                                Glycerin        10.0      10.0                                                Preservatives                                                                 Nuosept 95      4.0       4.0                                                 Premix          2.5       2.5                                                 M-Pyrol         2.4       2.4                                                 PVP 30          0.05      0.05                                                Troysan                                                                       Polyphase P-100 0.05      0.05                                                Citric Acid     0.3       0.3                                                 Dye                                                                           Acid Blue 93    2.3       --                                                  Acid Violet 19  --        0.7                                                 Acid Green 3    --        2.3                                                 ______________________________________                                                        Example 5 Example 6                                                           Green Ink Red Ink                                             Component       %         %                                                   ______________________________________                                        Deionized Water 63.7      63.7                                                Tamol SN        25.0      25.0                                                Glycerin        5.0       5.0                                                 Preservative                                                                  Nuosept 95      0.5       0.5                                                 Premix          2.5       2.5                                                 M-Pyrol         2.4       2.4                                                 PVP 30          0.05      0.05                                                Troysan                                                                       Polyphase P-100 0.05      0.05                                                Citric Acid     0.3       0.3                                                 Dye                                                                           Acid Green 3    2.0       --                                                  Basic Red 14    --        3.0                                                 ______________________________________                                    

The inks of examples 1 through 6 had acceptable working properties,including washability, and are especially suitable for overcolorelimination by an overcolor coloring composition containing a reducingagent. The black ink of Example 4 reddens somewhat after drying. The useof Tamol Sn in Example 5 improves washability of the acid green dye, butshifts the color of the dye. The inks of examples 5 and bleachcompletely and immediately and are completely washable. The ink ofexample 5 has a skin fugitivity of 0.5 and the ink of Example 6 has askin fugitivity of 0.

    ______________________________________                                        Overcolor Coloring ink Examples                                               ______________________________________                                                  Example 7    Example 8 Example 9                                              Pink Ink     Green Ink Blue Ink                                     Component %            %         %                                            ______________________________________                                        DI Water  42.75        42.47     42.96                                        Glycerin  5.00         5.00      5.00                                         Na.sub.2 SO.sub.3                                                                       10.20        10.20     10.20                                        NaOH (5N  11.05        11.05     11.05                                        Soln) 20%                                                                     Solution                                                                      Dowfax 3B2                                                                              30.00        30.00     30.00                                        Dye                                                                           Acid Red 388                                                                            1.00         --        --                                           Pyranine 120                                                                            --           0.43      --                                           Direct Blue 199                                                                         --           0.28      0.84                                         ______________________________________                                                  Example 10   Example 11                                                       Yellow Ink   Blue Ink                                               Component %            %                                                      ______________________________________                                        DI Water  42.05        37.75                                                  Glycerin  5.00         10.00                                                  Na.sub.2 SO.sub.3                                                                       10.20        10.20                                                  NaOH (5N  11.05        11.05                                                  Soln) 20%                                                                     Solution                                                                      Dowfax 3B2                                                                              30.00        --                                                     Dowfax 8390                                                                             --           30.00                                                  Polytergent BN                                                                          --           --                                                     Dye                                                                           Pyranine 120                                                                            1.30         --                                                     Direct Orange                                                                 102       0.40         --                                                     Acid Red 388                                                                            --           --                                                     Direct Blue 199                                                                         --           0.84                                                   ______________________________________                                    

The inks of examples 7-11 had acceptable working properties. The inks ofexamples 7 and 8 have a viscosity of 4.91 cps and pH of 12.3 and 12.2,respectively. The inks of examples 7-9 are completely washable from theskin by mere rinsing with water without soap. The inks of 7-10 have skinfugitivity values of 0, 0.5, 1.0, and 0, respectively, 6 and fabricfugitivity (E) values of 0, 0, 0.5, and 2.0.

In using the various above described overcolor coloring compositions andundercolor coloring compositions, a child could place a mark of theundercolor blue coloring composition on paper, perhaps to paint the sky.If the child wishes to add in a yellow sun, a green tree growing up intothe blue sky, and red flowers growing into the blue sky into thepicture, the child may easily use the above-indicated overcolor coloringink compositions, without tainting any of the colors. Alternatively, ifthe child draws a sun using the yellow overcolor coloring composition,he or she may draw in the sky using the blue undercolor ink right overthe yellow without spoiling the colors.

The multiple coloring composition system of the invention may also beformulated as a paint. When compositions of the invention are formulatedas a paint, such as a child's paint, they must necessarily be formulatedwith a higher viscosity to enable to the application of the of the paintwith a brush. This viscosity is achieved in two ways. In formulating anundercolor coloring composition, a binder may generally be added to thecomposition. This binder may be in the form of a modified starch such asSTADEX 140™ marketed by A. E. Staley Manufacturing Company. Binders aretypically used in amounts of from about 0% to about 25% by weight of thecomposition.

Additionally, paints may contain a thickener to provide body to thepaint. One suitable thickener is STAR-POL™ 560, a modified starchthickener, marketed by A. E. Staley Manufacturing Company. Anothersuitable thickener, especially for use in elevated pH compositions suchas the overcolor coloring composition of the invention is LAPONITE RDS™,a synthetic hectorite. The amount of thickener used depends upon theamounts of binder and other components used in the composition, althoughtypically about 1% to about 5% by weight thickener is used.

Paints may also contain a filler or extender. Fillers and extenders aregenerally solid particles added to paint compositions which provide bodyto the paint but which do not provide color. Common extenders are talcs,such as magnesium silicate hydrate, and clays and two suitable extendersfor compositions of the invention are TALCRON MP™ 45-26 marketed byPfizer Inc. and IMSIL A-108™. Extenders may be used in amounts of fromabout 0% to about 40% by weight of the composition. Where extenders orpigments are used in a paint, a dispersant may also be used to maintainthe solid particles dispersed in the paint. Dispersants, such asNOPCOSPERSE 44™, are typically used in amounts of from about 0.1% toabout 5%. Also, many paints optionally include a freeze/thaw protector.Freeze/thaw additives improve the stability of the paint over widelyvarying temperatures. One suitable freeze/thaw protector is propyleneglycol which is effective when used in compositions of the invention inamounts from about 1% to about 10% by weight, with the most preferredrange being from about 1.5% to about 6.5% by weight.

In a further embodiment of the present invention, a variety ofundercolor colors may be painted or otherwise applied on a substrate,such as paper, and the substrate, with these colors applied could besupplied to a child in combination with the overcolor coloringcomposition in the form of a paint or an ink in a marker. An appropriateovercolor coloring composition could then be applied onto the substratein areas where the child desired a change of color to produced thedesired color change.

From the foregoing description and examples, it is apparent that theobjects of the present invention have been achieved. While only certainembodiments have been set forth, alternative embodiments and variousmodifications will be apparent to those skilled in the art. These andother alternatives are considered equivalents and within the spirit andscope of the present invention. All patents and patent applicationsreferenced herein are hereby incorporated herein in their entirety byreference.

What is claimed is:
 1. A washable multiple coloring composition systemcomprising:(a) an undercolor aqueous coloring composition comprising acompatible surfactant in an amount sufficient to provide washability tosaid undercolor aqueous coloring composition and an undercolor dye whosecoloring ability is destroyed in the presence of a pH of about 10 orgreater; and (b) an overcolor aqueous coloring composition comprising acompatible surfactant in an amount sufficient to provide washability tosaid overcolor aqueous coloring composition, a colorant capable ofmaintaining its characteristic color in the presence of a pH of about 10or greater and an effective amount of a base sufficient to yield a pH ofsaid overcolor aqueous coloring composition of about 10 or greater. 2.The multiple coloring composition system of claim 1, said base beingpresent in an amount sufficient to yield a pH of said overcolor aqueouscoloring composition of from about 10 to about
 12. 3. The multiplecoloring composition system of claim 1, said surfactant in saidovercolor aqueous coloring composition being present in an amount fromabout 20% to about 55% by weight.
 4. The multiple coloring compositionsystem of claim 2, said base added in an amount of from about 0.1% toabout 20% by weight of said overcolor aqueous coloring composition. 5.The multiple coloring composition system of claim 1, wherein saidundercolor dye of said undercolor coloring composition is selected fromthe group consisting of polymethine dyes, triphenylmethane dyes, cyaninedyes, methine dyes, and azo dyes which are unstable in the presence of apH of about 10 or greater.
 6. The multiple coloring composition of claim5, wherein said undercolor dye of said undercolor coloring compositionis selected from the group consisting of Basic Blue 69, Basic Red 14,Basic Red 49, Acid Green 3, Acid Violet 19 and mixtures thereof.
 7. Themultiple coloring composition system of claim 1, wherein said colorantof said overcolor coloring composition is selected from the groupconsisting of, xanthene dyes, pthalocyanine dyes, and azo dyes which arestable in the presence of a pH of about 10 or greater.
 8. The multiplecoloring composition system of claim 1, wherein said colorant of saidovercolor coloring composition is selected from the group consisting ofAcid Red 52, Acid Red 87, Acid Red 92, Acid Red 388, Food Red 14, AcidGreen 26, Solvent Green 7, Direct Blue 199, and mixtures thereof.
 9. Themultiple coloring composition system of claim 1, wherein said overcoloraqueous coloring composition further comprises a reducing agent.
 10. Themultiple coloring composition system of claim 9, wherein said reducingagent is selected from the group consisting of hydrogen sulfide, sodiumsulfite, sodium hypochlorite and hydrogen peroxide.
 11. The multiplecoloring composition system of claim 1, wherein said base is selectedfrom the group consisting of ammonium hydroxide, sodium hydroxide andsodium carbonate.
 12. The multiple coloring composition system of claim1, wherein said undercolor and said overcolor coloring compositionsfurther comprise a humectant in an amount of from about 0% to about 30%by weight.
 13. The multiple coloring composition system of claim 1,wherein said undercolor and said overcolor coloring compositions furthercomprise a drying agent in an amount of from about 5% to about 30% byweight.
 14. The multiple coloring composition system of claim 1, whereinsaid colorant of said overcolor aqueous coloring composition is presentin an amount of from about 0.1% to about 15% by weight.
 15. The multiplecoloring composition system of claim 1, wherein said undercolor and saidovercolor coloring compositions further comprise a preservative.
 16. Themultiple coloring composition system of claim 15, wherein saidpreservative is present in said undercolor and said overcolor coloringcompositions in an amount of from about 0.1% to about 5% by weight. 17.A washable ink composition system comprising:(a) an undercolor aqueousink comprising a compatible surfactant in an amount sufficient toprovide washability and an undercolor dye whose coloring ability isdestroyed in the presence of a pH of about 10 or greater in an amount offrom about 0.1% to about 15% by weight of the undercolor ink; and (b) anovercolor aqueous ink comprising from about 20% to about 55% by weightof a compatible surfactant; from about 1% to about 20% by weight of saidovercolor ink of a reducing agent; from about 0.1% to about 10% byweight of said overcolor ink of a base; and from about 0.1% to about 15%by weight of said overcolor ink of an overcolor colorant which maintainsits characteristic color in the presence of a reducing agent and a pH ofabout 10 or greater.
 18. The ink composition system according to claim17, wherein said base is present in an amount of from about 0.1% toabout 20% by weight.
 19. The ink composition system according to claim17, wherein said undercolor dye and said overcolor colorant are eachpresent in an amount of from about 1% to about 6% by weight.
 20. Awashable color changing marking system comprising at least an undercolormarking instrument and an overcolor marking instrument, said undercolormarking instrument containing from about 20% to about 55% of acompatable surfactant and an undercolor ink composition comprising a dyewhose coloring ability is destroyed in the presence of a pH of about 10or greater, and said overcolor marking instrument containing anovercolor ink, said ink comprising(1) from about 20% to about 55% of acompatible surfactant; (2) from about 0.1% to about 10% by weight of abase; and (3) from about 0.1% to about 15% by weight of a colorant whichmaintains its characteristic color in the presence of a pH of about 10or greater.
 21. The marking system of claim 20, wherein said overcolorink further comprises a reducing agent.
 22. The marking system of claim21 wherein said reducing agent is sodium sulphite.
 23. The markingsystem of claim 20, wherein said base is sodium hydroxide.
 24. Themarking system of claim 21, wherein said system further comprises atleast a third marking instrument, said third marking instrumentcontaining an undercolor ink composition comprising a dye whose coloringability is destroyed in the presence of a reducing agent.
 25. Themarking system of claim 20, wherein said marker comprises and inkreservoir coupled to a nib.
 26. A washable paint composition systemcomprising:(a) an undercolor aqueous paint comprising from about 20% toabout 55% of a compatible surfactant and an undercolor dye whosecoloring ability is destroyed in the presence of a pH of about 10 orgreater; and (b) an overcolor aqueous paint comprising from about 20% toabout 55% of a compatible surfactant; from about 0.1% to about 20% byweight of a base; from about 0.1% to about 15% by weight of an overcolordye that maintains its characteristic color in the presence of a pH ofabout 10 or greater; and a thickener in an amount of from about 1% toabout 5% by weight.
 27. A washable coloring composition comprising(a)from about 20% to about 55% of a compatible surfactant; (b) from about0.1% to about 10% by weight of a base; (c) from about 1% to about 20% byweight of a reducing agent; and (d) from about 0.1% to about 15% byweight of a colorant which maintains its characteristic color in thepresence of both a pH of about 10 or greater and a reducing agent.
 28. Awashable multiple coloring composition system comprising:(a) a firstundercolor aqueous coloring composition comprising from about 20% toabout 55% by weight of a compatible surfactant and an undercolor dyewhose coloring ability is destroyed in the presence of a pH of about 10or greater; (b) a second undercolor aqueous coloring compositioncomprising from about 20% to about 55% by weight of a compatiblesurfactant and an undercolor dye whose coloring ability is destroyed inthe presence of a reducing agent; and (c) an overcolor aqueous coloringcomposition comprising from about 20% to about 55% by weight of acompatible surfactant, from about 0.1% to about 15% by weight of acolorant capable of maintaining its characteristic color in the presenceof a pH of about 10 or greater, an effective amount of a base sufficientto yield a pH of said overcolor aqueous coloring composition of about 10or greater, and from about 1% to about 20% by weight of a reducingagent.
 29. The multiple coloring composition system of claim 28, saidbase being present in an amount sufficient to yield a pH of saidovercolor aqueous coloring composition of from about 10 to about
 12. 30.A washable ink composition system comprising:(a) a first undercoloraqueous ink comprising from about 20% to about 55% by weight of acompatible surfactant and an undercolor dye whose coloring ability isdestroyed in the presence of a pH of about 10 or greater in an amount offrom about 0.1% to about 15% by weight of the undercolor ink; (b) asecond undercolor aqueous ink comprising from about 20% to about 55% byweight of a compatible surfactant and an undercolor dye whose coloringability is destroyed in the presence of a reducing agent; and (c) anovercolor aqueous ink comprising from about 20% to about 55% by weightof a compatible surfactant, from about 1% to about 20% by weight of saidovercolor ink of a reducing agent; from about 0.1% to about 10% byweight of said overcolor ink of a base; and from about 0.1% to about 15%by weight of said overcolor ink of an overcolor colorant which maintainsits characteristic color in the presence of a reducing agent and a pH ofabout 10 or greater.
 31. A washable color changing marking systemcomprising at least a first undercolor marking instrument and a secondundercolor marking instrument and at least one overcolor markinginstrument, said first undercolor marking instrument containing a firstundercolor ink composition comprising from about 20% to about 55% byweight of a compatible surfactant and a dye whose coloring ability isdestroyed in the presence of a pH of about 10 or greater, said secondundercolor marking instrument containing a second undercolor inkcomposition comprising from about 20% to about 55% by weight of acompatible surfactant and comprising an undercolor dye whose coloringability is destroyed in the presence of a reducing agent, and saidovercolor marking instrument containing an overcolor ink, said overcolorink comprising(1) from about 20% to about 55% by weight of a compatiblesurfactant; (2) from about 0.1% to about 10% by weight of a base; and(3) from about 0.1% to about 15% by weight of a colorant which maintainsits characteristic color in the presence of a pH of about 10 or greater,and from about 1% to about 20% by weight of a reducing agent and whereinsaid pH of said overcolor ink is about 10 or greater.
 32. The multiplecoloring composition system of claim 1, said surfactant of saidundercolor aqueous coloring composition being present in an amount offrom about 20% to about 55% by weight.
 33. The multiple coloringcomposition of claim 1, wherein said surfactant is an anionic surfactantselected from the group consisting of diphenyl oxide disulfonate andsodium naphthalene sulfonate.
 34. The multiple coloring composition ofclaim 17, wherein said surfactant is an anionic surfactant selected fromthe group consisting of diphenyl oxide disulfonate and sodiumnaphthalene sulfonate.
 35. The multiple coloring composition of claim20, wherein said surfactant is an anionic surfactant selected from thegroup consisting of diphenyl oxide disulfonate and sodium naphthalenesulfonate.
 36. The multiple coloring composition of claim 28, whereinsaid surfactant is an anionic surfactant selected from the groupconsisting of diphenyl oxide disulfonate and sodium naphthalenesulfonate.
 37. A washable multiple coloring composition systemcomprising:(a) an undercolor aqueous coloring composition comprising acompatible surfactant in an amount sufficient to provide washability tosaid undercolor aqueous coloring composition and an undercolor dye whosecoloring ability is destroyed in the presence of a reducing agent; and(b) an overcolor aqueous coloring composition comprising a compatiblesurfactant in an amount sufficient to provide washability to saidovercolor aqueous coloring composition, a colorant capable ofmaintaining its characteristic color in the presence of a reducingagent, and a reducing agent.
 38. The multiple coloring compositionsystem of claim 37, wherein said surfactant in said overcolor aqueouscoloring composition is present in an amount from about 20% to about 55%by weight.
 39. The multiple coloring composition system of claim 37,wherein said surfactant in said undercolor aqueous coloring compositionis present in an amount of from about 20% to about 55% by weight. 40.The multiple coloring composition system of claim 37, wherein saidsurfactant is an anionic surfactant.
 41. The multiple coloringcomposition system of claim 40, wherein said anionic surfactant isselected from the group consisting of diphenyl oxide disulfonate andsodium naphthalene sulfonate.
 42. The multiple coloring compositionsystem of claim 37, wherein said overcolor aqueous coloring compositionfurther comprises a base in an amount sufficient to elevate the pH ofsaid overcolor aqueous coloring composition to about 10 or greater. 43.The multiple coloring composition system of claim 42, wherein said baseis present in an amount of from about 0.1% to about 20% by weight ofsaid overcolor aqueous coloring composition.
 44. The multiple coloringcomposition system of claim 37, wherein said reducing agent is selectedfrom the group consisting of hydrogen sulfide, sodium sulfite, sodiumhypochlorite and hydrogen peroxide.
 45. The multiple coloringcomposition system of claim 37, wherein said reducing agent is presentin an amount of from about 1% to about 20%.
 46. The multiple coloringcomposition system of claim 37, wherein said undercolor dye of saidundercolor coloring composition is selected from the group consisting ofpolymethine dyes, triphenylmethane dyes, cyanine dyes, methine dyes, andazo dyes which are unstable in the presence of a of about 10 or greater.47. The multiple coloring composition system of claim 46, wherein saidundercolor dye of said undercolor coloring composition is selected fromthe group consisting of Basic Blue 69, Basic Red 14, Basic Red 49, AcidGreen 3, Acid Violet 19 and mixtures thereof.
 48. The multiple coloringcomposition system of claim 37, wherein said colorant of said overcolorcoloring composition is selected from the group consisting of xanthenedyes, phthalocyanine dyes, and azo dyes.
 49. The multiple coloringcomposition system of claim 48, wherein said colorant of said overcolorcoloring composition is selected from the group consisting of Acid Red52, Acid Red 87, Acid Red 92, Acid Red 388, Food Red 14, Acid Green 26,Solvent Green 7, Direct Blue 199, and mixtures thereof.
 50. A washableink composition system comprising:(a) an undercolor aqueous inkcomprising a compatible surfactant in an amount sufficient to providewashability and an undercolor dye whose coloring ability is destroyed inthe presence of a reducing agent in an amount of from about 0.1% toabout 15% by weight of the undercolor ink; and (b) an overcolor aqueousink comprising from about 20% to about 55% by weight of a compatiblesurfactant; and from about 0.1% to about 15% by weight of said overcolorink of an overcolor colorant which maintains its characteristic color inthe presence of a reducing agent.
 51. A washable color changing markingsystem comprising at least an undercolor marking instrument and anovercolor marking instrument, said undercolor marking instrumentcontaining from about 20% to about 55% of a compatible surfactant and anundercolor ink composition comprising from about 20% to about 55% of acompatible surfactant and from about 0.1% to about 15% by weight of acolorant which maintains its characteristic color in the presence of areducing agent.
 52. A washable paint composition system comprising:(a)an undercolor aqueous paint comprising from about 20% to about 55% of acompatible surfactant and an undercolor dye whose coloring ability isdestroyed in the presence of a reducing agent; and (b) an overcoloraqueous paint comprising from about 20% to about 55% of a compatiblesurfactant; from about 0.1% to about 15% by weight of an overcolor dyethat maintains its characteristic color in the presence of a reducingagent; and a thickener in an amount of from about 1% to about 5% byweight.